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Charles James, B. Smith Hopkins, and the Tangled Web of Element 61

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Charles James, B. Smith Hopkins, and the Tangled Web of Element 61 Bull. Hist. Chem., VOLUME 31, Number 1 (2006) 9 CHARLES JAMES, B. SMITH HOPKINS, AND THE TANGLED WEB OF ELEMENT 61 Clarence J. Murphy, East Stroudsburg University of Pennsylvania Introduction claimed they found an element that almost certainly does not exist in nature. The history of the search for and discovery of Element 61 is one of the most complex and confused of any of James and Hopkins the elements in the periodic table. Certainly no element has been “discovered” and named more times than 61. Two American chemists, Charles James (1) of the Uni- At least seven claims for discovery were made and 61 versity of New Hampshire and B. Smith Hopkins (2) of has been named at various times illinium, florentium, the University of Illinois were involved in the contro- cyclonium, and promethium. The story of element 61 is versies that surrounded claims of discovery for element also intimately connected with the development of the 61 in the 1920s. understanding of atomic structure and of the Periodic The conventional wisdom on Professor Jamesʼs Table, and of advances in science and technology in the contributions is probably best summarized by a quote late 19th and early 20th centuries. The story involves from an article on Element 61 by Gould, which appeared Roentgenʼs discovery of X-rays and Moseleyʼs use of in Chemical and Engineering News in 1949 (3): X-ray spectra to determine atomic numbers. It involves the more than one hundred-year effort to separate the rare When Hopkins made his announcement in March earths and to find a place for them in the Periodic Table. 1926, James and Fogg of the University of New Finally it involves the development of ion-exchange Hampshire had just completed their fractionation of ytterspar and had sent the 61-rich concentrate to Cork chromatography and research on the atomic bomb during at the University of Michigan for X-ray analysis. The World War II. Element 61 was named prometheum in results were reported in December, but by this time the 1946 by its discoverers Coryell, Marinsky, and Glendenin controversies over the other three claims were in full after the Titan Prometheus, who stole fire from the gods swing, and the fourth entry went almost unnoticed in and was sentenced to eternal torment for the crime, as spite of the fact that the evidence was perhaps better a warning that atomic energy could be the savior or the than that of any other claimant. Probably contributing destroyer of humankind. The spelling was later changed to this neglect was the fact that the announcement was to promethium by IUPAC. published in a relatively obscure journal (Proceedings of the National Academy of Sciences)…Seven lines of The story of Element 61 also involves highly the L series, falling between the corresponding lines competent, careful investigators who searched for and of elements 60 and 62, were observed in the X-ray spectrogram, which accompanied the announcement. 10 Bull. Hist. Chem., VOLUME 31, Number 1 (2006) To date, no other X-ray spectrogram of element 61 that element 61 was missing. Incidentally, Moseley ap- has been published, and while Jamesʼ work has never parently never received the sample of thulia or received been successfully repeated, neither has it been denied it after his paper was submitted because the space for or repudiated. thulium (69), in his list of atomic numbers is vacant. Gouldʼs view of Jamesʼs role in the element 61 contro- versy has been repeated by other authors (4), or James Why James published his paper on element 61 in the has been ignored entirely (5). Proceedings of the National Academy of Science has been puzzling, since almost all of his 60 papers were published The situation is actually much more complex as in the Journal of the American Chemical Society (13). revealed by scrapbooks kept by Marion E. James, wife The answer is provided in a letter to James from Arthur of Charles James (6) and recently catalogued by the B. Lamb, editor of the Journal of the American Chemical University of New Hampshire Archives. They contain Society. This letter dated April 26, 1926 reads (14): letters, which together with others in the University of Illinois Archives (7), shed light on the origins of Jamesʼ Dear Professor James: search for element 61 and his relationships with B. S. The enclosed manuscripts from Dr. Hopkins will, I Hopkins and W. A. Noyes. am sure, interest you. Dr. Hopkins is naturally very desirous of getting them published promptly, indeed in The instigation of Jamesʼ search for Element 61 the June number if possible. If you could give me your is most probably a letter from Sir William Ramsay to verdict on them promptly, I would be grateful. Charles James dated February 26, 1912 (8). In this let- Yours truly, ter he points out that there are a number of wide gaps in Arthur B. Lamb atomic weights between adjacent known elements which Dictated. may indicate a missing element. Among these gaps is one Manuscripts by Drs. Hopkins and Yntema, en- between neodymium and samarium. closed. Letters from Sir William Crookes (9) show that James received this letter at the time he was waiting for from early 1908 Crookes was analyzing rare earth the X-ray spectrum of his sample to be determined by samples spectroscopically in his private laboratory for Cork at the University of Michigan. He was now being James. One of these letters, written in 1913 indicates that asked to referee papers on the very subject he had been James was searching for a new element in a sample of working on for probably fourteen years. The papers ytterbium. Crookes writes, referring to a letter of April claimed discovery and proposed the name illinium for 2 from James (10): element 61 on the basis of evidence that seemed no better I shall be glad to photograph its (an ytterbium sample) than that which he had declined to publish several years spectrum and send you the results. I can point out to earlier. James apparently quickly gave a positive opinion you what impurities it contains, but the actual mea- because the two papers were published with the notations: surement of the lines in any new element is a very “Received April 26, 1925; Published June 5, 1925.” tedious job. I am afraid I cannot undertake to give more than an approximate measurement (say to five Evidently James then submitted his paper on Ele- figures) of any new lines. ment 61 to the Proceedings of the National Academy of A letter from H. E. G. Moseley to James, dated May 27, Science, to avoid any conflict of interest. Since none of 1914, in which he requests a sample of thulia to replace the authors was a member of the Academy, the identity the one which had been lost in the mail contains the of the transmitter has been a mystery. A letter dated lines (11): October 25, 1925 to James from Karl T. Compton in I am most interested to hear of your systematic search Zürich, Switzerland supplies the answer. The letter for the missing Nd-Sm element. I have been unsuc- reads in part (15): cessful in the few, rather rough, attempts to find the I have transmitted your very interesting paper on Ele- lines corresponding to it in the X-ray spectrum of a ment 61 to Professor E. B. Wilson, editor of the Proc. Nd-Sm mixture. of the Nat. Acad. I am sorry that the forwarding of This indicates that James had a systematic search for your letter has caused some delay. element 61 underway before the publication of Moseleyʼs The paper was published without further delay in second paper on atomic numbers (12), which showed the December, 1926 issue of the Proceedings. Bull. Hist. Chem., VOLUME 31, Number 1 (2006) 11 The Papers on Element 61 of Hopkins and results were published in a series of articles in the Bureau James of Standards Scientific Papers between 1921 and 1923. In one of these articles Kiess is quoted by Harris and It is perhaps useful to examine Hopkinsʼ and Jamesʼ Hopkins as stating (20): publications to determine their experimental procedures A third table contains 130 lines of unknown origin and the reasoning which led to the conclusion that they which are common to both spectra (neodymium and had discovered element 61. samarium). These lines are of unknown origin and may belong to the missing element of order No. 61… Hopkinsʼ publication con- On the basis of this evidence L. sists of two papers, “Observa- F. Yntema conducted an exten- tions on the Rare Earths XXII. sive fractionation of neodymium Element No. 61 Part One. Con- and samarium materials using centration and Isolation in Im- double magnesium nitrate salts. pure State,” by J. Allen Harris Because the solubilities of the with B. Smith Hopkins (16) double magnesium salts increase and “Observations on The Rare with atomic number, element 61 Earths XXII. Element No. 61 should concentrate in the frac- Part Two. X-Ray Analysis,” by tions between neodymium and J. Allen Harris with L. F. Yn- samarium. Examination of X-ray tema and B. S. Hopkins (17). spectra, however, failed to show The two papers bound together any evidence of element 61; but under the title “Element Number ultraviolet arc spectra of the pur- 61 (Illinium)” by Joseph Allen est samples of both neodymium Harris constituted Harrisʼs Ph.D. and samarium gave lines common thesis (18). to both elements, which were In a historical section of the somewhat stronger in intermedi- first paper it is stated that since ate samples.
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